Azo dyes of the 2,6-di(substituted) amino pyridine series

ABSTRACT

An azo dye of the general formula ##STR1## where A is cyano or carbamoyl, 
     R is hydrogen, alkyl or phenyl, 
     R 1  is hydrogen, bromine, chlorine or nitro, 
     R 2  is hydrogen, chlorine, bromine, nitro, methyl, trifluoromethyl, sulfamoyl, N-monoalkyl- or N,N-dialkylsulfamoyl (where alkyl is of 1 to 4 carbon atoms), or a sulfonic acid phenyl ester, methylphenyl ester, chlorophenyl ester or methoxyphenyl ester group, 
     R 3  is hydrogen or alkyl of 1 to 8 carbon atoms which may be interrupted by oxygen and may be substituted by hydroxyl, pyrrolidonyl, phthalimidyl, alkoxy of 1 to 8 carbon atoms, allyloxy, benzyloxy, phenylethoxy, phenoxy, methylphenoxy, chlorophenoxy, methoxyphenoxy, or optionally substituted arylsulfonyl, or is benzyl, phenylethyl or cyclohexyl, or is phenyl which is unsubstituted or substituted by chlorine, bromine, nitro, methyl, ethyl, methoxy, ethoxy, phenoxy or dialkylamino (where alkyl is of 1 to 4 carbon atoms), or is naphthyl, pyridyl, thienyl or furyl, 
     the substituents B 1  independently of one another are hydrogen or an aliphatic, cycloaliphatic, araliphatic, aromatic, heterocyclic or acyl radical and 
     B 2  is hydrogen or an aliphatic radical. 
     The dyes may be used for dyeing synthetic fibers, especially polyesters, and cellulose/polyester union fabrics, and give very fast dyeings.

SUMMARY OF THE INVENTION

The present invention relates to a dye of the general formula I ##STR2## where A is cyano or carbamoyl,

R is hydrogen, alkyl or phenyl,

R¹ is hydrogen, chlorine, bromine, or nitro,

R² is hydrogen, chlorine, bromine, nitro, methyl, trifluoromethyl, sulfamoyl, N-monoalkyl- or N,N-dialkylsulfamoyl (where alkyl is of 1 to 4 carbon atoms), or a sulfonic acid phenyl ester, methylphenyl ester, chlorophenyl ester or methoxyphenyl ester group,

R³ is hydrogen or alkyl of 1 to 8 carbon atoms which may be interrupted by oxygen and may be substituted by hydroxyl, pyrrolidonyl, phthalimidyl, alkoxy of 1 to 8 carbon atoms, allyloxy, benzyloxy, phenylethoxy, phenoxy, methylphenoxy, chlorophenoxy, methoxyphenoxy, or optionally substituted arylsulfonyl, or is benzyl, phenylethyl or cyclohexyl, or is phenyl which is unsubstituted or substituted by chlorine, bromine, nitro, methyl, ethyl, methoxy, ethoxy, phenoxy or dialkylamino (where alkyl is of 1 to 4 carbon atoms), or is naphthyl, pyridyl, thienyl or furyl,

the substituents B¹ independently of one another are hydrogen or an aliphatic, cycloaliphatic, araliphatic, aromatic, heterocyclic or acyl radical and B² is hydrogen or an aliphatic radical.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Alkyl R is, for example, methyl, ethyl, propyl, butyl or pentyl.

Radicals B¹ independently of one another are, for example, hydrogen, alkyl of 1 to 18 carbon atoms, alkyl of 2 to 8 carbon atoms which may be interrupted by ether-oxygen and is substituted by hydroxyl, alkoxy of 1 to 8 carbon atoms, benzyloxy, β-phenylethoxy, phenoxy, tolyloxy, cyclohexyloxy or cyano, cycloalkyl of 5 to 8 carbon atoms, hydroxycyclohexyl, β-hydroxyethoxycyclohexyl, polycycloalkyl of 7 to 12 carbon atoms, hydroxynorbornyl, hydroxymethylnorbornyl or hydroxyethylnorbornyl or chloromethylnorbornyl, phenylalkyl or tolylalkyl, where alkyl is of 1 to 4 carbon atoms, phenyl which is unsubstituted or substituted by chlorine, hydroxyl, methoxy, ethoxy, methyl, ethyl or hydroxyethoxy, allyl, pyrrolidonylalkyl, where alkyl is of 2, 3, 4 or 6 carbon atoms, carboxyalkyl, where alkyl is of 2 to 5 carbon atoms, ##STR3##

Examples of B² are the same aliphatic radicals as those given for B¹, and the same remarks apply, within the scope of the general definition, to R³. R³ may in addition be, for example, phenylsulfonylmethyl, tolylsulfonylmethyl, methoxyphenylsulfonylmethyl, chlorophenylsulfonylmethyl or bromophenylsulfonylmethyl.

Examples of individual radicals B¹, B² and R³ (to the extent that they fall under the general definition) are, in addition to those already mentioned:

1. Unsubstituted or substituted alkyl: CH₃, C₂ H₅, n- and i-C₃ H₇, n- and i-C₄ H₉, C₆ H₁₃, ##STR4## CH₂ CH₂ OH, (CH₂)₃ OH, ##STR5## (CH₂)₄ OH, (CH₂)₆ OH, ##STR6## (CH₂)₂ O(CH₂)₂ OH, (CH₂)₃ O(CH₂)₄ OH, (CH₂)₃ OC₂ H₄ OH, (CH₂)₂ CN, (CH₂)₅ CN, (CH₂)₆ CN, (CH₂)₇ CN, (CH₂)₂ O(CH₂)₂ CN, (CH₂)₃ O(CH₂)₂ CN, (CH₂)₂ O(CH₂)₂ O(CH₂)₂ CN, (CH₂)₃ OC₂ H₄ OCH₃, (CH₂)₃ OC₂ H₄ OC₂ H₅, (CH₂)₃ O(CH₂)₆ OH, (CH₂)₃ OC₂ H₄ OCH(CH_(3L) )₂, (CH₂)₃ OC₂ H₄ OC₄ H₉, (CH₂)₃ OC₂ H₄ OCH₂ C₆ H₅, (CH₂)₃ OC₂ H₄ OC₂ H₄ C₆ H₅, ##STR7## (CH₂)₃ OC₂ H₄ OC₆ H₅, ##STR8## the corresponding radicals which contain two or three of the groups --OC₂ H₄, ##STR9## CH₂ CH₂ OCH₃, CH₂ CH₂ OC₂ H₅, CH₂ CH₂ OC₃ H₇, CH₂ CH₂ OC₄ H₉, CH₂ CH₂ OC₆ H₅, (CH₂)₃ OCH₃, (CH₂)₃ OC₂ H₅, (CH₂)₃ OC₃ H₇, (CH₂)₃ OC₄ H₉, ##STR10## (CH₂)₃ OC₆ H₁₃, (CH₂)₃ OC₈ H₁₇, (CH₂)₃ O--, (CH₂)₃ OCH₂ C₆ H₅, (CH₂)₃ OC₂ H₄ C₆ H₅, (CH₂)₃ OC₆ H₅, ##STR11##

2. Substituted and unsubstituted cycloalkyl and polycycloalkyl: ##STR12##

3. Aralkyl: ##STR13## and corresponding radicals which contain C₆ H₄ CH₃ instead of C₆ H₅ ;

4. Substituted or unsubstituted phenyl: C₆ H₅, C₆ H₄ CH₃, C₆ H₃ (CH₃)₂, C₆ H₄ OCH₃, C₆ H₄ OC₂ H₅, C₆ H₄ OH, ##STR14## C₆ H₄ OCH₂ CH₂ OH and C₆ H₄ Cl;

5. CH₂ CH--CH₂, (CH₂)₂ COOH, (CH₂)₅ COOH and ##STR15## where n is 2, 3, 4 or 6, C₂ H₄ OCOCH₃, C₂ H₄ OCHO, C₂ H₄ OCOCH₃, (C₂ H₄ O)₂ COCH₃, (C₂ H₄ O)₂ CHO, (CH₂)₃ OCOCH₃, (CH₂)₃ OCHO and C₂ H₄ OCOC₂ H₄ COOH.

Further examples of R³ are CH₂ OCH₃, CH₂ OC₂ H₄, CH₂ OC₃ H₇, CH₂ OC₄ H₉, CH₂ OCH₂ CH═CH₂, CH₂ OCH₂ C₆ H₅ and CH₂ OC₆ H₅.

Examples of preferred substituents B¹ and B² are hydrogen, CH₃, C₂ H₅, n- and i-C₃ H₇, n- and i-C₄ H₉, C₆ H₁₃, CH₂ CH₂ OH, (CH₂)₃ OH, ##STR16## (CH₂)₄ OH, (CH₂)₆ OH, ##STR17## (CH₂)₂ O(CH₂)₂ OH, (CH₂)₃ O(CH₂)₂ OH, (CH₂)₃ O(CH₂)₄ OH, (CH₂)₃ O(CH₂)₆ OH, ##STR18## CH₂ CH₂ OCH₃, CH₂ CH₂ OC₂ H₅, CH₂ CH₂ OC₄ H₉, (CH₂)₃ OCH₃, (CH₂)₃ OC₂ H₅, (CH₂)₃ OC₃ H₇, (CH₂)₃ OC₄ H₉, ##STR19## (CH₂)₃ OC₂ H₄ OCH₃, (CH₂)₃ OC₂ H₄ OC₄ H₉, (CH₂)₃ OC₂ H₄ OC₆ H₅, ##STR20## CH₂ C₆ H₅, C₂ H₄ C₆ H₅, ##STR21## C₆ H₅, C₆ H₄ CH₃, C₆ H₄ OCH₃ and C₆ H₄ OC₂ H₄ OH.

Examples of radicals ##STR22## are pyrrolidino, piperidino, morpholino and N-methylpiperazino.

Examples of some preferred diazo components are: ##STR23##

On cellulose fibers, natural polyamides and synthetic nylons, polyesters and other synthetic fibers the dyes of the formula I give yellow to red dyeings with very good lightfastness, fastness to thermofixing and fastness to wet treatments. The tinctorial strength and the clear hues achievable with many of the dyes deserve particular mention.

Dyes of the formula given in claim 1 which are of particular industrial importance are those where

A is cyano or carbamoyl,

R is hydrogen or alkyl of 1 to 3 carbon atoms,

R¹ is hydrogen, chlorine, bromine or nitro,

R² is hydrogen, chlorine, bromine, nitro, methyl, trifluoromethyl, sulfamoyl, N-monosubstituted or N,N-disubstituted alkylsulfamoyl, where alkyl is of 1 to 4 carbon atoms, or a sulfonic acid phenyl ester, methylphenyl ester, chlorophenyl ester or methoxyphenyl ester group,

R³ is hydrogen or alkyl of 1 to 8 carbon atoms which is unsubstituted or substituted by hydroxyl, alkoxy of 1 to 8 carbon atoms, allyloxy, phenoxy, methylphenoxy, chlorophenoxy or methoxyphenoxy, or is benzyl, phenylethyl or cyclohexyl, or is phenyl which is unsubstituted or substituted by chlorine, bromine, nitro, methyl, ethyl, methoxy, ethoxy or phenoxy, or is naphthyl, pyridyl, thienyl or furyl, or is

    --X--(O--Y).sub.n OT

X is alkylene of 1 to 3 carbon atoms,

Y is alkylene of 2 or 3 carbon atoms,

n is 1 or 2,

T is hydrogen, alkyl of 1 to 4 carbon atoms, benzyl, phenylethyl, phenyl or tolyl,

B¹ is hydrogen, alkyl of 1 to 8 carbon atoms, alkyl of 2 to 8 carbon atoms which is substituted by hydroxyl, alkoxy of 1 to 8 carbon atoms, phenoxy, tolyloxy, phenyl, alkanoyloxy of 1 to 8 carbon atoms, alkoxycarbonyl (where alkoxy is 1 to 8 carbon atoms), alkylaminocarbonyloxy. (where alkyl is of 1 to 4 carbon atoms) or phenylaminocarbonyloxy, or cyclohexyl, norbornyl, allyl, phenyl, tolyl or chlorophenyl, or

    --Y--(O--Y).sub.n --OT

and

B² is hydrogen or alkyl of 1 to 4 carbon atoms which is unsubstituted or substituted by hydroxyl or by alkoxy of 1 to 4 carbon atoms.

Preferably, R is hydrogen or methyl and B² is hydrogen. A further preferred combination is where R is H and A is CONH₂.

The preferred meanings of B¹ are those given above.

The dye of the formula I may be prepared by reacting a diazonium compound of an amine of the formula ##STR24## with a coupling component of the formula ##STR25## Diazotization and coupling are carried out in accordance with conventional methods.

In the Examples which follow, parts and percentages are by weight, unless stated otherwise.

EXAMPLE 1

24 parts of the compound of the formula (1) (see above) are dissolved in 250 parts by volume of glacial acetic acid and 50 parts by volume of propionic acid. 32 g of 40% strength nitrosylsulfuric acid are added dropwise at 0°-5° C. and the mixture is then stirred for 2 hours at 0°-5° C. The excess nitrous acid is then destroyed in the conventional manner by adding urea.

The diazotized mixture thus obtained is introduced, at 0°-5° C., into a mixture obtained by dissolving 28 parts of 2-(ω-hydroxy-butoxyamino)-6-amino-3-cyano-4-methylpyridine in 500 parts of water by means of 15 parts of 10 N hydrochloric acid and adding 250 parts of ice.

Sufficient saturated sodium acetate solution is then added dropwise to the coupling mixture to produce complete coupling at a pH of from 4 to 5.

The resulting dye is filtered off, washed with water and dried at 100° C. The powder obtained gives a yellow solution in N-methylpyrrolidone or dimethylformamide and on polyester or nylon fabrics gives yellow dyeings of very good lightfastness and great fastness to thermofixing.

EXAMPLE 2

A solution of 27 parts of 2,6-bis-(methoxyethylamino)-3-cyano-4-methylpyridine in 100 parts by volume of glacial acetic acid is added, at 0°-5° C., to the diazotized mixture obtained as described in Example 1, paragraph 1, and 500 parts by volume of a saturated sodium acetate solution are then added.

The resulting dye is filtered off, washed with water and ethanol and dried at 100° C. The product is a yellow powder which gives a yellow solution in N-methylpyrrolidone. On polyester or cotton fabrics or polyester/cotton union fabrics, yellow prints of very good lightfastness and wetfastness are obtained.

EXAMPLE 3

32 parts of 40 percent strength nitrosylsulfuric acid are added, at 0°-5° C., to a solution of 28 parts of the compound of the formula 2 (see list of diazo components on page 5) in 100 parts by volume of concentrated sulfuric acid. After stirring for 2 hours at 0°-5° C., the excess nitrous acid is destroyed in the conventional manner by adding urea.

The resulting mixture is run gradually, at 0°-5° C., into a mixture of 27 parts of 2,6-bis-(methoxyethylamino)-3-cyano-4-methylpyridine, 3,000 parts by volume of N-methylpyrrolidone and 500 parts of ice.

After completion of coupling, the dye is filtered off, washed with ethanol and dried. The dark red powder gives a red solution in N-methylpyrrolidone and produces fast bluish red prints on polyester and on cotton.

EXAMPLE 4

14.8 parts of the diazo component of the formula ##STR26## are stirred into a mixture of 70 parts of glacial acetic acid, 10 parts of propionic acid and 5 parts by volume of sulfuric acid and after cooling to 5° C., 14 parts of 40% strength nitrosylsulfuric acid are added whilst cooling. The diazotized mixture is then stirred for 70 minutes at 0°-5° C. Thereafter, the diazonium salt solution is run into a solution, cooled to 0°-5° C., of 8.05 parts of 2,6-bis-ethylamino-3-cyano-4-methylpyridine in 600 parts by volume of water and 8 parts by volume of concentrated hydrochloric acid. After raising the pH of the mixture to 2.0-2.2 by means of dilute sodium acetate solution or sodium hydroxide solution, the coupling reaction is soon complete. The mixture is heated to 60°-70° C. and the product is filtered off and washed salt-free with water at 60°-70° C. After drying, 22.5 parts of a dark brown powder, which gives a bluish red solution in N-methylpyrrolidone, are obtained.

The dye has the formula ##STR27## The dye gives fast bluish red prints on polyester and on cotton, and dyes polyester by the HT process, at 125°-140° C., in fast bluish red hues.

EXAMPLE 5

12.7 parts of the compound of the formula ##STR28## are introduced, at 0°-5° C., into a mixture of 26.4 parts of 96-98% strength sulfuric acid, 13.5 parts of 42% strength nitrosylsulfuric acid, 20 parts of propionic acid and 120 parts of glacial acetic acid. The mixture is then stirred for 3.5 hours at 0°-5° C. The finished diazonium salt mixture is run into a solution, cooled to 0°-5° C., of 11.6 parts of 2,6-bis-methoxypropylamino-3-cyano-4-methylpyridine in 600 parts by volume of water and 10 parts by volume of concentrated hydrochloric acid. The coupling reaction is completed rapidly on raising the pH to 2.0-2.2 by means of dilute sodium hydroxide solution. The mixture is stirred for 1 hour and then heated to 70° C., and the dye which has precipitated is filtered off, washed salt-free with water, and dried. 23 parts of a yellowish red powder of the formula ##STR29## are obtained.

The dye gives a red solution in N-methylpyrrolidone and dyes polystyrene in lightfast golden yellow to orange hues.

EXAMPLE 6

14.0 parts of the diazo component of the formula ##STR30## are dissolved in 200 parts by volume of glacial acetic acid at 50°-55° C. 2 parts of an emulsifier and 150 parts of ice are added. The mixture is then acidified with 18 parts by volume of concentrated hydrochloric acid at 0°-5° C., after which 21 parts by volume of a 23% strength aqueous sodium nitrite solution are added dropwise. The diazotization reaction is complete after stirring for 2 hours and a clear solution is obtained, which is combined with a solution, cooled to 5° C., of 17.6 parts of 2,6-bis-methoxypropylamino-3-cyano-4-methylpyridine in 600 parts by volume of water and 13 parts by volume of concentrated hydrochloric acid. After raising the pH to 2, the mixture is stirred for 30 minutes, after which it is heated to 70° C. and the dye which has precipitated is filtered off, washed salt-free with water and dried. 31.5 parts of a dark brown powder of the formula ##STR31## are obtained. This product gives a bluish red solution in dimethylformamide and produces fast bluish red prints on polyester and on cotton. Polyester can be dyed with the dye by the HT process or thermosol process.

The following dyes can be obtained by methods similar to those described in the preceding Examples:

    __________________________________________________________________________                                         Hue on poly-                                                                   ester or                                   No.                                                                               Diazo component                                                                         Coupling component      cotton                                     __________________________________________________________________________     7  Diazo component of the formula 2                                                         ##STR32##              red                                        8  Diazo component of the formula 2                                                         ##STR33##              red                                        9  Diazo component of the formula 2                                                         ##STR34##              red                                        10 Diazo component of the formula 4                                                         ##STR35##              yellow                                     11 Diazo component of the formula 4                                                         ##STR36##              yellow                                     12 Diazo component of the formula 4                                                         ##STR37##              yellow                                     13 Diazo component of the formula 1                                                         ##STR38##              yellow                                     14 Diazo component of the formula 1                                                         ##STR39##              yellow                                     15 Diazo component of the formula 1                                                         ##STR40##              yellow                                     16 Diazo component of the formula 3                                                         ##STR41##              yellow                                     17 Diazo component of the formula 3                                                         ##STR42##              yellow                                     __________________________________________________________________________

                                      TABLE 1                                      __________________________________________________________________________      ##STR43##                                                                                                              Hue on                                                                         poly-                                 No.                                                                               R.sup.1     R.sup.2      R.sup.3    n ester                                 __________________________________________________________________________     18 CH.sub.2 CH.sub.2 OCOCH.sub.3                                                              CH.sub.2 CH.sub.2 OCOCH.sub.3                                                               C.sub.6 H.sub.5                                                                           0 yellow                                19 "           "            "          1 red                                   20 CH.sub.2 CH.sub.2 OCOC.sub.2 H.sub.5                                                       CH.sub.2 CH.sub.2 OCOC.sub.2 H.sub.5                                                        "          0 yellow                                21 "           "            "          1 red                                   22 CH.sub.2 CH.sub.2 OCOOC.sub.2 H.sub.5                                                      CH.sub.2 CH.sub.2 OCOOC.sub.2 H.sub.5                                                       "          0 yellow                                23 "           "            "          1 red                                   24 CH.sub.2 CH.sub.2 OCONHC.sub.6 H.sub.5                                                     CH.sub.2 CH.sub.2 OCONHC.sub.6 H.sub.5                                                      "          0 yellow                                25 "           "            "          1 red                                   26 CH.sub.2 CH.sub.2 OCONHC.sub.4 H.sub.9                                                     CH.sub.2 CH.sub.2 OCONHC.sub.4 H.sub.9                                                      "          0 yellow                                27 "           "            "          1 red                                   28 CH.sub.2 CH.sub.2 OCH.sub.3                                                                CH.sub.2 CH.sub.2 OCH.sub.3                                                                 "          0 yellow                                29 H           "            "          0 yellow                                30 "           (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OC.sub.6 H.sub.5                                          ##STR44## 0 yellow                                31 H           (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OC.sub.6 H.sub.5                                         CH.sub.3   1 red                                   32 "           "            C.sub.2 H.sub.5                                                                           1 red                                   33 "           (CH.sub.2).sub.3 O(CH.sub.2).sub.4 OH                                                       "          1 red                                   34 "           "            (CH.sub.2).sub.2 OCH.sub.3                                                                1 red                                   35 "           (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OC.sub.6 H.sub.5                                         "          1 red                                   36 CH.sub.2 CH.sub.2 OCH.sub.3                                                                "            "          1 red                                   37 "           "            C.sub.2 H.sub.5                                                                           1 red                                   38 CH.sub.2 CH.sub.2 OH                                                                       "            "          1 red                                   39 CH.sub.2 CH.sub.2 OCH.sub.3                                                                "            C.sub.6 H.sub.5                                                                           1 red                                   40 "           C.sub.4 H.sub.9 (n)                                                                         "          1 red                                   41 "           (CH.sub.2).sub.2 OCH.sub.3                                                                  CH.sub.2 CH.sub.2 OCH.sub.3                                                               1 red                                   42 "           "            CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                        1 red                                   43 (CH.sub.2).sub.3 OCH.sub.3                                                                 (CH.sub.2).sub.3 OCH.sub.3                                                                  "          1 red                                   44 "           "            CH.sub.2 CH.sub.2 OCH.sub.3                                                               1 red                                   45 "           "            CH.sub.2 CH.sub.2 C.sub.6 H.sub.5                                                         1 red                                   46 "           "            CH hd 3    1 red                                   47 "           C.sub.4 H.sub.9 (n)                                                                         C.sub.6 H.sub.5                                                                           1 red                                   48 CH.sub.2 CH.sub.2 OCH.sub.3                                                                (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OC.sub.6 H.sub.5                                          ##STR45## 1 red                                   49 "           CH.sub.2 CH.sub.2 OCH.sub.3                                                                 "          1 red                                   50 (CH.sub.2).sub. 3 OCH.sub.3                                                                (CH.sub.2).sub.3 OCH.sub.3                                                                  "          1 red                                   51 CH.sub.2 CH.sub.2 OCH.sub.3                                                                "            "          1 red                                   52 C.sub.4 H.sub.9 (n)                                                                        C.sub.4 H.sub.9 (n)                                                                         "          1 red                                   53 C.sub.2 H.sub.5                                                                            C.sub.3 H.sub.7 (n)                                                                         (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OC.sub.6                                    H.sub.5    1 red                                   54 "           C.sub.2 H.sub.5                                                                             "          0 yellow                                55 C.sub.3 H.sub.7 (n)                                                                        "            "          0 yellow                                56 "           "            "          1 red                                   57 CH.sub.2 CH.sub.2 OCH.sub.3                                                                (CH.sub.2).sub.3 OCH.sub.3                                                                  C.sub.2 H.sub.5                                                                           1 red                                   58 "           "            CH.sub.2 CH.sub.2 CH.sub.3                                                                1 red                                   59 "           CH.sub.2 CH.sub.2 OCH.sub.3                                                                 "          1 red                                   60 (CH.sub.2).sub.3 OCH.sub.3                                                                 (CH.sub.2).sub.3 OCH.sub.3                                                                  "          1 red                                   61                                                                                 ##STR46##  "            "          1 red                                   62 "                                                                                           ##STR47##   "          1 red                                   63                                                                                 ##STR48##                                                                                  ##STR49##   C.sub.2 H.sub.5                                                                           1 red                                   64 (CH.sub.2).sub.3 OCH.sub.3                                                                 (CH.sub.2).sub.3 OCH.sub.3                                                                  C.sub.4 H.sub.9 (n)                                                                       1 red                                   65 "           "                                                                                            ##STR50## 1 red                                   66 "           "                                                                                            ##STR51## 0 yellow                                67 "           "            "          1 red                                   68 C.sub.4 H.sub.9 (n)                                                                        C.sub.4 H.sub.9 (n)                                                                         "          1 red                                   69 H                                                                                           ##STR52##   CH.sub.2 CH.sub.2 OCH.sub.3                                                               0 yellow                                70 CH.sub.2 CH.sub.2 OCOCH.sub.3                                                              CH.sub.2 CH.sub.2 OCOCH.sub.3                                                               (CH.sub.2).sub.2 O(CH.sub.2).sub.2 OC.sub.6                                    H.sub.5    1 red                                   71 "           "            "          0 yellow                                72 (CH.sub.2).sub.3 OCH.sub.3                                                                 (CH.sub.2).sub.3 OCH.sub.3                                                                   ##STR53## 0 yellow                                73 "           "            "          1 red                                   __________________________________________________________________________

                                      TABLE 2                                      __________________________________________________________________________      ##STR54##                                                                                                                                 Hue                                                                            on                                                                             cot-               No.                                                                               R.sup.1                                                                           R.sup.2                                                                           R.sup.3  R.sup.4                                                                               R.sup.5      R.sup.6                                                                             R.sup.7                                                                           R.sup.8       ton                __________________________________________________________________________     74 Br Br (CH.sub.2).sub.2 OCH.sub.3                                                              (CH.sub.2).sub.2 OCH.sub.3                                                            (CH.sub.2).sub.2 OCH.sub.3                                                                  CN   CH.sub.3                                                                          C.sub.6 H.sub.5                                                                              yel-                                                                           low                75 "  "  "        "      H            "    H  "             yel-                                                                           low                76 H  H  "        "      (CH.sub.2).sub.2 OCH.sub.3                                                                  "    "  (CH.sub.2).sub.2 O(CH.sub.2)                                                   .sub.2 OC.sub.6 H.sub.5                                                                      yel-                                                                           low                77 "  "  (CH.sub.2).sub.3 OCH.sub.3                                                              H      (CH.sub.2).sub.3 OCH.sub.3                                                                  "    CH.sub.3                                                                           ##STR55##    yel- low           78 O.sub.2 N                                                                         "  "        (CH.sub.2).sub.2 OCH.sub.3                                                            (CH.sub.2).sub.2 OCH.sub.3                                                                  "    "  C.sub.2 H.sub.5                                                                              red                79 "  Cl "        H      (CH.sub.2).sub.3 OCH.sub.3                                                                  "    "  C.sub.6 H.sub.5                                                                              dull                                                                           blu-                                                                           ish                                                                            red                80 "  Br "        "      "            "    "  "             dull                                                                           blu-                                                                           ish                                                                            red                81 "  H  "        "      "            CONH.sub.2                                                                          H  "             dull                                                                           blu-                                                                           ish                                                                            red                82 NO.sub.2                                                                          NO.sub.2                                                                          "        (CH.sub.2).sub.3 OCH.sub.3                                                            H            CN   CH.sub.3                                                                          "             vio-                                                                           let                83 O.sub.2 N                                                                         H  C.sub.2 H.sub.5                                                                         H      C.sub.2 H.sub.5                                                                             CONH.sub.2                                                                          H  (CH.sub.2).sub.2 O(CH.sub.2)                                                   .sub.2 OC.sub.6 H.sub.5                                                                      dull                                                                           blu-                                                                           ish                                                                            red                84 "  "  "        "      "            CN   CH.sub.3                                                                          (CH.sub.2).sub.2 OCH.sub.2                                                     C.sub.6 H.sub.5                                                                              red                85 "  "  "        "      "            "    "  (CH.sub.2).sub.2 OCH.sub.2                                                     CH.sub.2 C.sub.6 H.sub.5                                                                     red                86 "  "  "        "      "            "    "  (CH.sub.2).sub.2 OC.sub.6                                                      H.sub.5       red                87 "  "  (CH.sub.2).sub.3 OCH.sub.3                                                              "      (CH.sub.2).sub.3 OCH.sub.3                                                                  "    "  CH.sub.2C.sub.6 H.sub.5                                                                      red                88 "  "  (CH.sub.2).sub.2 OCH.sub.3                                                              "      (CH.sub.2).sub.2 OCH.sub.3                                                                  "    "  "             red                89 "  "  (CH.sub.2).sub.3 OCH.sub.3                                                              "      (CH.sub.2).sub.3 OCH.sub.3                                                                  "    "                                                                                  ##STR56##    red                90 H  H                                                                                  ##STR57##                                                                              H                                                                                      ##STR58##   "    "  C.sub.6 H.sub.5                                                                              red                91 CF.sub.3                                                                          H  (CH.sub.2).sub.2OCH.sub.3                                                               H      (CH.sub.2).sub.2OCH.sub.3                                                                   "    "  "             gold-                                                                          en                                                                             yel-                                                                           low                92 CF.sub.3                                                                          H  (CH.sub.2).sub.3OCH.sub.3                                                               H      (CH.sub.2).sub.3OCH.sub.3                                                                   "    "  "             yel-                                                                           low-                                                                           ish                                                                            or-                                                                            ange               93 CF.sub.3                                                                          H  H        H                                                                                      ##STR59##   "    "  "             gold- en yel-                                                                  ow                 __________________________________________________________________________

                                      TABLE 3                                      __________________________________________________________________________      ##STR60##                                                                     No.                                                                               T.sup.2 R.sup.3       R.sup.7                                                                           R.sup.1 R.sup.2 Hue                                __________________________________________________________________________     94 CF.sub.3                                                                               C.sub.6 H.sub.5                                                                              H  CH.sub.2 CH.sub.2 OCH.sub.3                                                            CH.sub.2 CH.sub.2 OCH.sub.3                                                            golden                                                                         yellow                             95 (C.sub.2 H.sub.5).sub.2 NO.sub.2 S                                                     "             CH.sub.3                                                                          "       "       orange                             96 "       "             "  (CH.sub.2).sub.3 OCH.sub.3                                                             (CH.sub.2).sub.3 OCH.sub.3                                                             "                                  97 "       "             "  C.sub.4 H.sub.9 (n)                                                                    C.sub.4 H.sub.9 (n)                                                                    "                                  98 C.sub.6 H.sub.5 O.sub.3 S                                                              CH.sub.3      "  "       "       "                                  99 "       C.sub.2 H.sub.5                                                                              "  (CH.sub.2).sub.3 OCH.sub.3                                                             (CH.sub.2).sub.3 OCH.sub.3                                                             "                                  100                                                                               O.sub.2 N                                                                              CH.sub.2 OCH.sub.3                                                                           "  "       "       bluish                             101                                                                               "       "             H  "       "       "                                  102                                                                               "       "             C.sub.2 H.sub.5                                                                   "       "       "                                  103                                                                               "       "             CH.sub.3                                                                          C.sub.4 H.sub.9 (n)                                                                    C.sub.4 H.sub.9 (n)                                                                    "                                  104                                                                               "       "             "  C.sub.3 H.sub.7 (n)                                                                    C.sub.3 H.sub.7 (n)                                                                    "                                  105                                                                               O.sub.2 N                                                                              CH.sub.2 OCH.sub.3                                                                           CH.sub.3                                                                          C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                        bluish                                                                         red                                106                                                                               "       CH.sub.2 OC.sub.6 H.sub.5                                                                    "  "       "       bluish                                                                         red                                107                                                                               "       "             "  C.sub.4 H.sub.9 (n)                                                                    C.sub.4 H.sub.9 (n)                                                                    bluish                                                                         red                                108                                                                               "       CH.sub.2 CH.sub.2 OC.sub.3 H.sub.7 (n)                                                       "  "       "       red                                109                                                                               "       "             "  C.sub.3 H.sub.7 (n)                                                                    C.sub.3 H.sub.7 (n)                                                                    "                                  110                                                                               "       "             "  C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                        "                                  111                                                                               "       "             "  (CH.sub.2).sub.3 OCH.sub.3                                                             (CH.sub.2).sub.3 OCH.sub.3                                                             bluish                                                                         red                                112                                                                               "       Ch.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                           Ch.sub.3                                                                          C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                        red                                113                                                                               "       "             "  C.sub.3 H.sub.7 (n)                                                                    C.sub.3 H.sub.7 (n)                                                                    "                                  114                                                                               "       "             "  "       (CH.sub.2).sub.3 OCH.sub.3                                                             "                                  115                                                                               "       "             "  CH.sub.2 CHCH.sub.2                                                                    CH.sub.2 CHCH.sub.2                                                                    "                                  116                                                                               "       "             "  C.sub.4 H.sub.9 (n)                                                                    C.sub.4 H.sub.9 (n)                                                                    "                                  117                                                                               "       "             "  (CH.sub.2 9.sub.2 OCH.sub.3                                                            (CH.sub.2).sub.3 OCH.sub.3                                                             "                                  118                                                                               "       "             "  C.sub.2 H.sub.5                                                                        C.sub.6 H.sub.13 (n)                       119                                                                               "       "             "  "       C.sub.6 H.sub.13 (i)                                                                   "                                  120                                                                               O.sub.2 N                                                                              CH.sub.2 OCH.sub.3                                                                           CH.sub.3                                                                          C.sub.2 H.sub.5                                                                        C.sub.6 H.sub.13 (i)                                                                   red                                121                                                                               "       CH.sub.2 OC.sub.2 H.sub.5                                                                    "  C.sub.3 H.sub.7 (n)                                                                    C.sub.3 H.sub.7 (n)                                                                    red                                122                                                                               "       "             "  C.sub.4 H.sub.9 (n)                                                                    C.sub.4 H.sub.9 (n)                                                                    "                                  123                                                                               "       "             "  (CH.sub.2).sub.3 OCH.sub.3                                                             (CH.sub.2).sub.3 OCH.sub.3                                                             "                                  124                                                                               "                                                                                       ##STR61##    "  "       "       "                                  125                                                                               "       CH.sub.2 Ch.sub.2 OC.sub.4 H.sub.9 (n)                                                       "  "       "       "                                  126                                                                               "       "             "  C.sub.2 h.sub.5                                                                        C.sub.2 H.sub.5                                                                        "                                  127                                                                               "       "             "  C.sub.2 H.sub.7 (n)                                                                    C.sub.3 H.sub.7 (n)                                                                    "                                  128                                                                               "       CH.sub.2 CH.sub.2 OC.sub.6 H.sub.13 (n)                                                      "  C.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                        "                                  129                                                                               "                                                                                       ##STR62##    "  "       "       "                                  130                                                                               "       "             "  C.sub.3 H.sub.7 (n)                                                                    C.sub.3 H.sub.7 (n)                                                                    "                                  131                                                                               "       "             "  (CH.sub.2).sub.3 OCH.sub.3                                                             (CH.sub.2).sub.3 OCH.sub.3                                                             "                                  132                                                                               "       H             "  C.sub.4 H.sub.9 (n)                                                                    C.sub.4 H.sub.9 (n)                                                                    "                                  133                                                                               "       "             "  (CH.sub.2).sub.2 OCH.sub.3                                                             (CH.sub.2).sub.3 OCH.sub.3                                                             "                                  134                                                                               "       CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OC.sub.4 H.sub.9 (n)                                    CH.sub.3                                                                          C.sub.2 H.sub.5/ C.sub.2 h.sub.5                                                       "                                          135                                                                               "       "             "  C.sub.3 H.sub.7 (n)                                                                    C.sub.3 H.sub.7 (n)                                                                    "                                  __________________________________________________________________________      ##STR63##                                                                     Ex.                                                                               X           R           R.sup.1    R.sup.2                                                                              hue                                __________________________________________________________________________     144                                                                               SO.sub.2 N(C.sub.2 H.sub.5).sub.2                                                          C.sub.6 H.sub.5                                                                            C.sub.2 H.sub.4 C.sub.6 H.sub.5                                                           C.sub.2 H.sub.4 C.sub.6 H.sub.5                                                      orange                             145                                                                               "           "           C.sub.2 H.sub.4 OCH.sub.3                                                                 "     "                                  146                                                                               "           "           (CH.sub.2).sub.3 OC.sub.2 H.sub.4 OC.sub.6                                     H.sub.5    H     "                                  147                                                                               Cl          "           "          H     "                                  148                                                                                ##STR64##  "           C.sub.2 H.sub.4 OCH.sub.3                                                                 C.sub.2 H.sub.4 OCH.sub.3                                                            "                                  149                                                                               "           "           C.sub.3 H.sub.6 OCH.sub.3                                                                 C.sub.3 H.sub.6 OCH.sub.3                                                            "                                  150                                                                               H                                                                                           ##STR65##  "          "     yellow                             151                                                                               H           CH.sub.2 SO.sub.2 C.sub.6 H.sub.5                                                          "          "     "                                  152                                                                               NO.sub.2    "           "          "     red                                153                                                                               "           CH.sub.3    C.sub.2 H.sub.4 C.sub.6 H.sub.5                                                           C.sub.2 H.sub.4 C.sub.6 H.sub.5                                                      "                                  154                                                                               "           C.sub.2 H.sub.5                                                                            "          "     "                                  155                                                                               "           CH.sub.2 OCH.sub.3                                                                         "          "     "                                  156                                                                               "           C.sub.2 H.sub.4 OCH.sub.3                                                                  "          "     "                                  157                                                                               "           C.sub.2 h.sub.4 OC.sub.3 H.sub.7 (n)                                                       "          "     "                                  158                                                                               "           "           C.sub.2 h.sub.4 OCONHC.sub.4 h.sub.9 (n)                                                  C.sub.2 h.sub.5                                                                      "                                  159                                                                               "           C.sub.2 h.sub.4 OCH.sub.3                                                                  "          "     "                                  160                                                                               "           C.sub.2 H.sub.4 OC.sub.3 H.sub.7 (n)                                                       C.sub.2 h.sub.4 OCONHC.sub.6 h.sub.5                                                      "     "                                  __________________________________________________________________________     No.                                                                               T.sup.2                                                                            R.sup.3         R.sup.7                                                                           R.sup.1                                                                               R.sup.2    hue                                __________________________________________________________________________     161                                                                               O.sub.2 N                                                                          CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OC.sub.4 H.sub.9 (n)                                      CH.sub.3                                                                          C.sub.4 h.sub.9 (n)                                                                   C.sub.4 H.sub.9 (n)                                                                       red                                162                                                                               "   "               "  (CH.sub.2).sub.3 OCH.sub.3                                                            (CH.sub.2).sub.3 OCH.sub.3)                                                               "                                  163                                                                               "   CH.sub.2 CH.sub.2 (OCH.sub.2 CH.sub.2).sub.2 OC.sub.4 H.sub.9                                  CH.sub.3                                                                          C.sub.2 H.sub.5                                                                       C.sub.2 H.sub.5                                                                           "                                  164                                                                               "   "               "  C.sub.3 H.sub.7 (n)                                                                   C.sub.3 h.sub.7 (n)                                                                       "                                  165                                                                               "   "               "  C.sub.4 H.sub.9 (n)                                                                   C.sub.4 H.sub.9 (n)                                                                       "                                  166                                                                               "   C.sub.6 h.sub.5 "  H      (CH.sub.2).sub.3 O(CH.sub.2).sub.2                                             OC.sub.6 H.sub.5                                                                          "                                  167                                                                               Cl  "               "  "      (CH.sub.2).sub.3 O(CH.sub.2).sub.4                                                        golden                                                                         yellow                             168                                                                               Br  "               "  (CH.sub.2 9.sub.3 OCH.sub.3                                                           (CH.sub.2).sub.3 OCH.sub.3                                                                orange                             __________________________________________________________________________ 

What is claimed as new and intended to be covered by Letters Patent is:
 1. A compound of the formula ##STR66## where A is cyano or carbamoyl,R is hydrogen or alkyl of 1 to 3 carbon atoms, R¹ is hydrogen, chlorine, bromine or nitro, R² is hydrogen, chlorine, bromine, nitro, methyl, trifluoromethyl, sulfamoyl, N-monoalkyl- or N,N-dialkylsulfamoyl, where alkyl is of 1 to 4 carbon atoms, or a sulfonic acid phenyl ester, methylphenyl ester, chlorophenyl ester or methoxyphenyl ester group, R³ is selected from the group consisting of hydrogen, alkyl of 1 to 8 carbon atoms which is unsubstituted or substituted by hydroxyl, alkoxy of 1 to 8 carbon atoms, allyloxy, phenoxy, methylphenoxy, chlorophenoxy, methoxyphenoxy, or optionally substituted arylsulfonyl; benzyl; phenylethyl; cyclohexyl; phenyl which is unsubstituted or substituted by chlorine, bromine, nitro, methyl, ethyl, methoxy, ethoxy or phenoxy; naphthyl; pyridyl; thienyl; furyl; and

    --X--(O--Y).sub.n --OT

whereinX is alkylene of 1 to 3 carbon atoms, Y is alkylene of 2 or 3 carbon atoms, n is 1 or 2, T is hydrogen, alkyl of 1 to 4 carbon atoms, benzyl, phenylethyl, phenyl or tolyl, B¹ is hydrogen, alkyl of 1 to 8 carbon atoms, alkyl of 2 to 8 carbon atoms which is substituted by hydroxyl, alkoxy of 1 to 8 carbon atoms, phenoxy, tolyloxy, phenyl, alkanoyloxy of 1 to 8 carbon atoms, C₁ to C₄ alkoxycarbonyl, C₁ to C₄ alkylaminocarbonyloxy or phenylaminocarbonyloxy, or cyclohexyl, norbornyl, allyl, phenyl, tolyl or chlorophenyl, or

    --Y--(O--Y).sub.n --OT and

B² is hydrogen or alkyl of 1 to 4 carbon atoms which is unsubstituted or substituted by hydroxy or by alkoxy of 1 to 4 carbon atoms.
 2. A compound as claimed in claim 1, where A is cyano.
 3. A compound as claimed in claim 1, where R is hydrogen or methyl.
 4. A compound as claimed in claim 1, where R¹ is hydrogen, chlorine or nitro and R² is hydrogen or chlorine.
 5. A compound as claimed in claim 1 where R³ is selected from the group consisting of alkyl of 1 to 4 carbon atoms; alkyl of 1 to 3 carbon atoms which is substituted by alkoxy of 1 to 8 carbon atoms; phenyl which is unsubstituted or substituted by chlorine or methyl.
 6. A compound as claimed in claim 1, where B¹ is hydrogen, alkyl of 2 to 6 carbon atoms, allyl, alkyl of 2 or 3 carbon atoms which is substituted by alkoxy of 1 to 4 carbon atoms, phenylethyl, cyclohexyl or

    Y--O--Y--OT.sup.1

T¹ is alkyl of 1 to 4 carbon atoms, benzyl, phenylethyl, phenyl or tolyl and Y has the stated meaning.
 7. A compound as claimed in claim 1, of the formula ##STR67## where T² is hydrogen, chlorine or nitro and B¹ and R³ have the stated meanings.
 8. A compound as claimed in claim 1, of the formula ##STR68##
 9. A compound as claimed in claim 1, of the formula ##STR69##
 10. A compound as claimed in claim 1, of the formula ##STR70##
 11. A compound as claimed in claim 1, of the formula ##STR71##
 12. A compound as claimed in claim 1, of the formula ##STR72##
 13. A compound as claimed in claim 1, of the formula ##STR73##
 14. A compound as claimed in claim 1, of the formula ##STR74## 